Manufacture of melamine



Nov. l0, 1942.

V. L. KING MANUFACTURE OF MELAMINE Filed July 1K0, 1940 WASH W TIR INVEWOR. l//C'OP ./f//S/G,

ATTORNEY Patented Nov. l0, 1942 l UNITED STATE s PATENT OFFICE,

ascissa MANUFACTURE OF MELAMINE vicm- L. King, nonna amr, N. J., assigner t American Cyanamid Company, New York, N, Y., a corporation of Maine Application July 10, 1940, Serial c. 344,038

6 Claim (CL 26o-248) manufacture of resins'and clear and haze-free.,

melamine-formaldehyde lacquers.

Y It is known that a melamine product of high purity can be obtained by heating a mixture of about i part of cyanamide or dicyandiamide with from 1-2 parts of liquid ammonia in an autoclave, with or without the addition of anhydrous *methanol or other diluents to reduce the autoclave pressure. In ordinary commercial manu'- facture it has been the practice, after the heating is completed, to discharge the contents of the autoclave through a filter which separates the solid melamine product from the liquid ammonia` or other solvent mixture, and then to wash the solids collected on the filter with water. When thisl procedure is followed it is necessary'to reerystallize the resulting melamine product from boiling water, with or without the addition of caustic soda solution, if a pure product is desired.

cases the product obtained by simply washingthe filter cake from the autoclave charge once or twice with water has analyzed as high as 96-98% melamine. analysis available at the present time are based primarily on the dinerential solubility of melamine in hot and cold water, and are therefore only accurate within a few percent, there is every indication that va pure melamine is produced by the above process. It is thereforel very surprising to find that resins and lacquers made by condensing melamine from this source with formaldehyde are inferior in quality to those prepared4 from melamine manufactured by other and less eflicient processes.

Upon investigating the reasons why melamine prepared by the above described autoclave process is less well for resin manufacture than melamine from other sources, I found that the autoclave product exhibited a considerably higher alkalinity upon solution in hot water. Careful investigation has led me to believe that this alkalinity is due to the presence of one or more intermediate conversion products of cyanamide and/or dicyandiamide in the melamine, although it should be understood that my invention is not dependent upon the accuracy of this identification. The intermediate conversion products of cyanamide and dicyandiamide are guanidine,v biguanide and guanylurea, and my linvestigation has led me to believe that small amounts of one or more of these compounds are formed by side reactions during themelamine formation in the autocmve. Whatever the impurities may be,

however, they are basic in character, not com-l pletely removed from a solid melamine product by ordinary washing of the filter cake, and are a serious detriment to the quality of melamineformaldehyde lacquers containing them.

MY invention relates principally to a modification of the above described autoclave method for preparing melamine which I have found will avoid a product containing the above impurities. My new process will produce a melamine substantially free from guanidine, biguanide and/or guanylurea that can be converted into high-grade melamine-formaldehyde resins and lacquers. I \have found that such a melamine product is obtained when the' melamine content of the auto- `ave is washed before it is permitted to collect the form oi' a. solid4 cake such as is formed wh' n the contents' of the melamine autoclave are 'disc rged upon or through a filter. Apparently the separations, of tlie melamine from the ammoiamethanoi mixture or other solvent in the y autoclave in the-form of a filter cake results in an bsorp' on or adsorption of the alkaline impurities b solid melamine particles in such a lxnA erto be extremely'dimcult or impossible to r ove by ordinary washing procedures. By

. wasl'iing the melamine product before the ainmonia or `ammonia-methanol mixture is completely drained of! this adsorption is avoided and a product is obtained which is well suited for lacquermanufacture. l .The simplest method of avoiding the initial formation; of a cake of solid melamine is to dis- I charge the entire contents of the autoclave directly into a quantity of cold or lukewarm water, or into aqueous solutions or other solvents for the alkaline impurities such as ethyl alcohol or other organicV solvents, and this constitutes the preferred procedure in practicing my invention.

Other mechanical methods may also be used to discharge the autoclave without cake formation,- such as discharging the autoclave mixture into a spray-drying chamber in countercurrent contact with a rising stream of hot or cold gases or discharging a mixture containing melamine and liquid ammonia into a chamber so large that the melamine may settle gradually as a ne powder,

it being understood that in either case the product is washed before it is permitted to cake together.

-. Ashas been stated, the essential factor is the avoidance of a solid cake of -unwashed melamine product from the autoclave, and any suitable method may be used to obtain this result.

After the solid content of the autoclave has been discharged into water or other similar liquid media, it is whed by agitation and can then be safely collected on a filter and washed with water or other solvents in the usual manner. Surprising as it may seem, I have found that the stell Vof discharging the ventire contents of the autoclave, both solid, liquid and gaseous, directly into a body of water prior to iiltration is in itself suilicient to insure the production or a melamine product useful for lacquer manufacture instead of the alkaline' product containing guanidine and/or guanylurea that forms resins and lacquers of inferior quality. Once this step has been taken, thev usual procedure ofy nltering, washing the product with water and drying at high temperatures may be followed safely.

. The manipulative features of my invention Will' be illustrated in greater detail with reference to i 4the accompanying drawing, the single figure lof f which is a iiow sheet illustrating diagrammati- "callyva preferred modidcation thereof. Gn this owsheet. l indicates diagrammatically the autoclave in which the conversion of dcyandiamide J to melamine is carried out. This autoclave prefarabi! consists of a pressure'resistant vessel of of a solution of dicyandiamide in about an equal weight' of ammonia, with or without the addition of anhydrous methanol or other suitable diluent, is prepared in the mixing tank 2 and charged 'large capacity equipped with internal nestingcoils and with en agitator. A charge consisting into the autoclave. A suitable heating medium -such as high pressure steam is then passed through the heating coils of the autoclave and the charge is heated at temperatures of 120- 2202 C., and preferably at i60-200 C., for several hours or until the desired melamine product has been formed.

According to the principles of my invention, v

the Aentireautoclave charge is then blown directly linto a drowning tank 3, which is a large closed tank in which hasA been placed a quantity of water sumcient to form a pumpable slurry with the melamine product and preferably also sumcient to dissolve all the ammonia. Suitable cooling means are also preferably provided in this tank, in order that the temperature of its contents may be kept at a sufilciently low temperature to prevent the solution of too much of the melamine.v

' During the heating cycle in the autoclave a second batch of the dicyandiamide-liquid ammonia solutioncan be prepared in the mixing tank 2, and 'as soon as the autoclave is discharged this second batch can be pumped in and the autoclave again heated.

umn 6 is a solution containing small amounts of melamine dissolved in the drowning tank d, any

unreacted dicyandiamide and all the guanidine,

guanylurea or other alkaline lay-products that were formed in the autoclave. This liquor is preferably pumped to a drier 9, which may be a steam heated or direct fired vacuum concentrator, in which its content of solid material is recovered. This dried mixture of dicyandiamide, l

melamine and guanidine or guanylurea may then be added to the mixing tank during the preparetion of further charges for the autoclave.

` The invention will be illustrated in greater detail by the following specic examples. It should be understood, however, that these examples are given primarily for purposes of illustration andl that the invention in its broader aspects is not limited thereto.-

Example 1 A solution of -parts by weight of dicyandiamide in a mixture of 4 parts liquid anhydrous ammonia and 3.2 parts anhydrous methanol was charged into an autoclave, heated to 180 C. during l hour-and held at this temperature for l hour longer. The charge was then cooled to 100 C. and discharged at a pressure of 800 lbs/sq. in.

directly into a vessel containing 100 parts of water maintained at a temperature of 40 C. or lower.

The contents of the vessel, which were violently agitated by the pressure discharge, were allowed to settle.; the supernatant liquid was decanted and charged Ainto a stripping column for recovery of the ammonia and methanol, and the solid residue was again washed with 67 parts of water. This was vdecanted od and the resulting granular melamine was sucked free of adhering water on a vacuum nlter and dried in en oven at Per cent Melamine 94.9' Dcyandiamide 0.6 Cold water insolubles 4.5

In ythe meantime the slurry in the tank 3 is pumped intojthe'l filter press 4 with continuous agitation to prevent sedimentation. The nitrate leaving the nlter press through the line Sis passed to a stripping column 6 while the melamine on the .-iilter cloth, after being washed with fresh water. is charged into a drier and is obtained as a melamine suitable for resin and lacquer .manufacture.

' It is evident from the flow sheet that this modiication of my invention is well suited for the re- .l

covery and reuse of all the materials used in the process. Thewash water from the iilter press und returned to the drowning tank 3 to receive l the next batch ofv melamine while the ltrate isl heated in the stripping column 8 to separate out ammonia or a mixture of ammonia and methanol l dr other alcohol if a diluent was used in the autoclave. This ammonia or ammonia-alcohol mixstorage tank I from which a portion of it is returned to the mixing tank 2 for the preparation` of further hatches. lThe stripped liquor from the base-of the colcan be collected in a wash water storage tank 8 ture is preferably condensed and collected ina C. The product analyzed No' guanidine or guanylurea was found.

126 gra-mspf the above batch of melamine were mixed with 405.5 grams of 37% aqueous formaldehyde solution and440 grams of anhydrous butanol and the mixture was heated to boiling in -free lacquer was obtained, indicating that the melamine was free from guanidine and guanyl- Eample 2 Another batch of melamine was prepared ex- I.

actly as described in Example 1 except that the 'charge after cooling to 100 C. was discharged through a closed filter vessel containing a ne wire screen. The iilter cake which collected on the screenl was Washed with sufficient water to A' remove all the ammonia and was then dried in the oven at 110 C.

` 21,26 grams of this batch were reacted with tion with xylene, soon set up to an almost solicll gummy mass and was valueless as a lacquer.

Example 3 1465 pounds of dicyandiamide were dissolved in 2637 pounds of alcohol-ammonia solution, analyzing 54% ammonia and 46% methanol. This charge was pumped into a large autoclave and heated'to 180-200 C. for several hours 4at a pressure of 1600-1900 lbs./sq. in.

The autoclave charge was then blown into a quenching tank containing 6000 lbs. of water during a period of about 15 minutes. The solution in the quenching tank was then agitated and cooled by recirculation through a cooler until the temperature 'was lowered suillciently to reduce excessive losses of melamine, while retaining dicyandiamide in solutionI a temperature range of 40-:70 C. being suitable, and was then filtered in a lter press. 'I'he mother liquor was passed through a stripping column in which the alcohol and ammonia were recovered and the remaining water was then evaporated. The residue consisting of dicyandiamide, guanidine, and small amounts of melamine was then ready to be reintroduced into the autoclave with the next batch.

The melamine 4in the filter press Was washed with about 6000 lbs. of water Which-was then placed in the quenching tank to drown the discharge of the next batch of melamine from the autoclave. By reusing the wash Water in this manner it was possible to prevent loss of melamine dissolved. from the filter press.

After the washing in the filter press was complete the batch was spread out and dried at temperatures of about 100 C. A pure white product was obtained which exhibited a pH in water solution of 7.9 and analyzed 95.3% melamine, 0.6% dicyandiamide and 4.1%'insolubles. A butylated melamine-formaldehyde lacquer prepared from this material by the procedure described in Example 1 was clear, haze-free, and of excellent` quality.

Example 4 0.5% by-weight of guanylurea carbonate was added to 126 grams of the batch of melamine described in Example 3, and the mixture was then reacted with aqueous formaldehyde and butanol bythe procedure described in Example 1. The product, after dilution with xylene, soon set up to a gummy mass and was of no value as a lacquer, which proves that even small quantities of guanylurea are extremely harmful to the melamine product.

Example 5.

To 124.75 grams of the batch of melamine described in Example 3 was added 1.25 (1%)' grams of guanidine carbonate, and the mixture was then reacted with aqueous formaldehyde and butanol by the procedure described in Example 1. By the time the mixture was nearly dehydrated, as shown by a boiling point of 100 C. at atmospheric pressure, a large lpart of the resin had precipitated fromsolution in the butanol. This resinous precipitate would not dissolve in butanol sion products of the type of guanidine, biguanideV and guanylurea has been formed and washing this product with a liquid solvent for said impurities which does not dissolve substantial amounts of melamine before it is permitted to collect in the form of a solid cake.

2. A process for the manufacture of melamine suitable for lacquer manufacture which comprises heating a member of the group consisting of cyanamide and dicyandiamide in a solvent comprising anhydrous ammonia until a melamine product containing alkaline intermediate conversion products of the type of guanidine, biguanide and guanylurea has been formed and washing this productwith water before it is permitted to collectin the form of a solid cake.

3. A process for the manufacture of melamine suitable for lacquer manufacture which comprises heating a member of the group consisting of cyanamide and dicyandiamide and a solvent comprising anhydrous ammonia in an autoclave until a melamine product containing alkaline intermediate conversion products of the type of guanidine, biguanide and guanylurea has been formed and discharging the contents of the autoclave directly into a body of a liquid solvent for said impurities which does not dissove substantial amounts of melamine.

4. A process for the manufacture of melamine suitable for lacquer manufacture which comprises heating a member of the group consisting or' cyanamide and dicyandiamide and a solvent comprising anhydrous ammonia in an autoclave un- 1 5. A process for the manufacture of melamine which comprises the steps of heating a member of the group consisting of cyanamide and 'dicyandiamide and a solvent comprising liquid ammonia in an autoclave until a melamine product has been formed, discharging the contents of the autoclave directly into -a body of water to dissolve out impurities, filtering the resulting slurry. stripping the nitrate and recovering the ammonia therefrom, and evaporating the water from the stripped filtrate to recover its content oi' solid material.

6. A process for the manufacture of melamine which comprises the steps of heating a member of the group consisting of cyanami'de and dicyandiamide and a solvent comprising liquid ammonia in an autoclave until a melamine product autoclave directly into a body of water, filtering the resulting slurry and washing the melamine with water, and'discharging into the wash water autoclave.

VICTOR L. KING. 

